Method of producing hot-dip aluminum-based alloy-coated steel sheet

ABSTRACT

Provided is (i) a hot-dip Al-based alloy-coated steel sheet which includes a coated layer having a surface on which fine spangles are stably and sufficiently formed and which has a beautiful surface appearance due to the fine spangles thus formed on the surface of the coated layer, and (ii) a method of producing such a hot-dip Al-based alloy-coated steel sheet. The hot-dip Al-based alloy-coated steel sheet includes: a substrate steel sheet; and a hot-dip aluminum-based alloy coated layer which is formed on a surface of the substrate steel sheet and which contains boron at an average concentration of not less than 0.005 mass % and contains potassium at an average concentration of not less than 0.0004 mass %.

TECHNICAL FIELD

The present invention relates to a hot-dip Al-based alloy-coated steelsheet and a method of producing the hot-dip Al-based alloy-coated steelsheet. More specifically, the present invention relates to (i) a hot-dipAl-based alloy-coated steel sheet which has spangles having a minutesize and has a beautiful surface appearance due to such spangles, and(ii) a method of producing such a hot-dip Al-based alloy-coated steelsheet.

BACKGROUND ART

A hot-dip aluminum-based alloy-coated steel sheet (hereinafter referredto as a “hot-dip Al-based alloy-coated steel sheet”) includes a steelsheet whose surface is coated with an alloy, which contains aluminum(Al) as a main component, by a hot-dip method so that the steel sheetcan have higher corrosion resistance and/or higher heat resistance. Sucha hot-dip Al-based alloy-coated steel sheet has been widely used mainlyfor members that are required to have heat resistance, such as exhaustgas members of automobiles and members of combustion devices.

Note that the hot-dip Al-based alloy-coated steel sheet has a coatedlayer having a surface on which a spangle pattern appears, the spanglepattern being formed due to dendrites, which are structures obtained bysolidification of Al. The spangle pattern is a characteristic geometricpattern or a flower pattern, and each region (i.e., spangle) of thespangle pattern is constituted by dendrites.

A spangle grows during solidification of Al after coating. Growth of thespangle progresses as below. First, the nucleus of the spangle (i.e.,spangle nucleus) occurs. Then, a primary dendrite arm grows from thespangle nucleus. Subsequently, a secondary dendrite arm develops fromthe primary dendrite arm. Growth of such dendrite arms stops due to acollision between adjacent spangles. It follows that presence of morespangle nuclei in the coated layer causes an increase in number ofspangles. This causes each spangle to have a minute size.

The presence of such a spangle does not adversely affect a quality(e.g., corrosion resistance) of the hot-dip Al-based alloy-coated steelsheet. Note, however, that in the market, a hot-dip Al-basedalloy-coated steel sheet is preferred which has spangles having a minutesize and thus has a surface skin having an inconspicuous spanglepattern.

Under the circumstances, proposed is, for example, a method of producinga hot-dip aluminum-zinc alloy-coated steel sheet which includes a coatedlayer made of an aluminum-zinc alloy. According to this method, for thepurpose of formation of fine spangles, titanium (Ti), zirconium (Zr),niobium (Nb), boron (B), a boride such as aluminum boride (AlB₂ orAlB₁₂), titanium carbide (TiC), titanium boride (TiB₂), or titaniumaluminide (TiAl₃) is added to a coating bath so that more substanceseach acting as a spangle nucleus are obtained. Such a method isdisclosed in, for example, Patent Literatures 1 to 3.

CITATION LIST Patent Literatures

[Patent Literature 1]

Japanese Patent Application Publication Tokukai No. 2004-115908(Publication date: Apr. 15, 2004)

[Patent Literature 2]

Japanese Patent Application Publication Tokukai No. 2006-22409(Publication date: Jan. 26, 2006)

[Patent Literature 3]

Japanese Patent No. 3751879 (Publication date: Dec. 16, 2005)

[Patent Literature 4]

Japanese Patent No. 5591414 (Publication date: Sep. 17, 2014)

SUMMARY OF INVENTION Technical Problem

Note, however, that use of the above method to produce a hot-dipAl-based alloy-coated steel sheet has the following problems.

Specifically, since aluminum (having a specific gravity of 2.7) is oneof the lightweight metals, molten aluminum is lower in specific gravitythan an aluminum-zinc alloy (having a specific gravity of 7.1). Thus,any of substances, such as Ti, titanium carbide (TiC), titanium boride(TiB₂), and titanium aluminide (TiAl₃), which are higher in specificgravity than a hot-dip Al-based alloy-coating bath, easily precipitatesinto a bath bottom, so that it is difficult for such a substance to beuniformly dispersed in the hot-dip Al-based alloy-coating bath. Thiscauses a problem of difficulty in stable formation of fine spangles onsurfaces of hot-dip Al-based alloy-coated steel sheets which arecontinuously produced as in an industrial continuous operation.

Meanwhile, B and aluminum boride (AlB₂ or AlB₁₂) are less different inspecific gravity from an aluminum bath and thus are less likely toprecipitate into a bath bottom. Note, however, that, as compared with,for example, TiB₂, B and aluminum boride (AlB₂ or AlB₁₂) areunfortunately bring about a less satisfactory effect of finer spangles.

For example, Patent Literature 4 discloses, as a B-containing hot-dipAl-based alloy-coated steel sheet, a hot-dip Al-based alloy-coated steelsheet which contains B at a concentration of 0.002 mass % to 0.080 mass%. Note, however, that according to the technique disclosed in PatentLiterature 4, B which is unevenly distributed over a surface of a coatedlayer of a hot-dip Al-based alloy-coated steel sheet allows the coatedlayer to be more slidable against a mold, and consequently allows thecoated layer to be more resistant to galling. It follows that PatentLiterature 4 fails to disclose that fine spangles are formed so that ahot-dip Al-based alloy coated layer has a beautiful surface appearance.

The present invention has been made in view of the problems, and anobject of the present invention is to provide (i) a hot-dip Al-basedalloy-coated steel sheet which includes a coated layer having a surfaceon which fine spangles are stably and sufficiently formed and which hasa beautiful surface appearance due to the fine spangles thus formed onthe surface of the coated layer, and (ii) a method of producing such ahot-dip Al-based alloy-coated steel sheet.

Solution to Problem

The inventors of the present invention carried out a diligent study andfinally accomplished the present invention by finding that, as comparedwith a hot-dip Al-based alloy-coated steel sheet obtained with use of acoating bath to which B or aluminum boride (AlB₂ or AlB₁₂) is addedalone or titanium boride (TiB₂) and titanium aluminide (TiAl₃) areadded, a hot-dip Al-based alloy-coated steel sheet obtained with use ofa hot-dip Al-based alloy-coating bath containing both boron (B) andpotassium (K) in proper amounts exhibits a more remarkable effect offiner spangles.

That is, a hot-dip aluminum-based alloy-coated steel sheet in accordancewith an embodiment of the present invention includes: a substrate steelsheet; and a hot-dip aluminum-based alloy coated layer which is formedon a surface of the substrate steel sheet and which contains boron at anaverage concentration of not less than 0.005 mass % and containspotassium at an average concentration of not less than 0.0004 mass %.

Advantageous Effects of Invention

The present invention brings about an effect of providing (i) a hot-dipAl-based alloy-coated steel sheet which includes a coated layer having asurface on which fine spangles are stably and sufficiently formed andwhich has a beautiful surface appearance due to the fine spangles thusformed on the surface of the coated layer, and (ii) a method ofproducing such a hot-dip Al-based alloy-coated steel sheet.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an optical photomicrograph of a state in which the outermostsurface of a hot-dip Al-based alloy-coated steel sheet in accordancewith an embodiment of the present invention has been polished so that adendrite structure is made observable.

DESCRIPTION OF EMBODIMENTS

The following description will discuss an embodiment of the presentinvention. Note that, unless otherwise specified, the present inventionis not limited to the following description, which is provided so thatsubject matters of the present invention are better understood. Notealso that a numerical expression such as “A to B” as used herein means“not less than A and not more than B”.

First, the following description will schematically discuss knowledge ofthe present invention before discussing a hot-dip Al-based alloy-coatedsteel sheet in accordance with an embodiment of the present inventionand a method of producing such a hot-dip Al-based alloy-coated steelsheet.

(Schematic Description of Knowledge of Present Invention)

As described earlier, a spangle pattern formed due to dendrites commonlyappears on a surface of a hot-dip Al-based alloy coated layer. In orderthat such a spangle pattern is made inconspicuous, various approacheshave been taken. The spangle pattern can be made inconspicuous by, forexample, a method of carrying out a surface treatment as a posttreatment, e.g., carrying out skin-pass rolling many times aftercoating. However, such a method needs to be carried out with use of amajor apparatus or by a special process. This results in an increase inproduction cost.

In view of the above problem, a method has been proposed in which thespangle pattern is made inconspicuous by causing each spangle to have aminute size. In order to cause spangles to have a minute size, it isonly necessary to cause spangle nuclei which are formed at an earlystage of growth of the spangles to be highly dense. That is, thespangles can have a minute size by heterogeneous nucleation of spanglenuclei.

For example, known is a technique in which a substrate steel sheet isdipped in and taken out of a coating bath, and then fine mist or finemetal oxide powder is sprayed over a surface of an unsolidified coatedlayer. Note, however, that such a technique may (i) prevent, due toflapping of a steel sheet in a continuous hot-dip aluminum-coating line,spangles from being stably made finer and/or (ii) necessitate anapparatus for carrying out a spraying process and an apparatus formonitoring the spraying process.

In view of the above problems, as described earlier, a technique hasbeen proposed in which a substance acting as a spangle nucleus is addedto a coating bath. According to this technique, fine spangles areobtained by dipping a substrate steel sheet in a coating bath whosecomponents have been adjusted. Thus, this technique is low in cost andhighly convenient. Note, however, that use of such a technique toproduce a hot-dip aluminum-coated steel sheet causes such problems asdescribed earlier.

Under the circumstances, the inventors of the present invention carriedout detailed research on how various components that can be added to acoating bath influence fine spangles of a hot-dip Al-based alloy-coatedsteel sheet. As a result, the inventors found that a coating bathcontaining both B and K brings about a remarkable effect of finerspangles. That is, as compared with a hot-dip Al-based alloy-coatedsteel sheet obtained with use of a coating bath containing B or K alone,a hot-dip Al-based alloy-coated steel sheet obtained with use of acoating bath containing both B and K allows spangle nuclei formed on asurface of a coated layer to be denser. In particular, the researchrevealed that, as compared with a hot-dip Al-based alloy-coated steelsheet obtained with use of a coating bath to which B or aluminum boride(AlB₂ or AlB₁₂) is added alone or titanium boride (TiB₂) and titaniumaluminide (TiAl₃) are added, a hot-dip Al-based alloy-coated steel sheetobtained with use of a hot-dip Al-based alloy-coating bath containing Bat a concentration of not less than 0.005 mass % and K at aconcentration of not less than 0.0004 mass % exhibits a more remarkableeffect of finer spangles.

A specific mechanism by which a coating bath containing both B and Kenhances an effect of finer spangles is still unclear. However, it isclear that, as compared with a coating bath to which B or aluminumboride is added alone, a coating bath containing both B and K even invery small amounts brings about a more remarkable effect of finerspangles. It has been known that B is enriched (unevenly distributed)over a surface of a coated layer. However, a coating bath containing Balone is insufficient to bring about a satisfactory effect of finerspangles. In view of this, examples of the mechanism by which a coatingbath containing both B and K enhances the effect of finer spanglesinclude a mechanism in which B and K form clusters and the clusters areunevenly distributed over a surface of a coated layer so as to eachserve as a spangle nucleus.

Meanwhile, in a case where a coating bath contains both B and K but anamount in which the coating bath contains K is not excessive, (i) aneffect, brought about by a hot-dip Al-based alloy coated layer, ofimproving corrosion resistance (red rust resistance) of a steel sheetand (ii) intrinsic workability of an Al-coated layer are maintained asin the case of a coating bath not containing both B and K.

The above knowledge of the present invention is novel in the field ofhot-dip Al-based alloy-coated steel sheets, and the knowledge is greatin terms of the following points. According to an embodiment of thepresent invention, by adjusting a composition of a hot-dip Al-coatingbath, it is possible to easily and stably produce a hot-dip Al-basedalloy-coated steel sheet which has spangles whose size has been madesufficiently minute and which has a beautiful surface skin due to suchspangles. Furthermore, B and K, which are neither rare metals nor heavymetals, are abundant in the natural world and are harmless to humanbodies. Moreover, B and K are less likely to precipitate into the bottomof a hot-dip Al-based alloy-coating bath. This makes it possible tostably produce hot-dip Al-based alloy-coated steel sheets by anindustrial continuous operation. Thus, in another aspect, an embodimentof the present invention makes it possible to provide (i) a hot-dipAl-based alloy-coated steel sheet which can be produced at low cost,which is highly suitable for industrial and practical use, and which hasspangles having a minute size and has a beautiful surface appearance dueto such spangles, and (ii) a method of producing such a hot-dip Al-basedalloy-coated steel sheet.

The foregoing description has schematically discussed the knowledge ofthe present invention. Next, a hot-dip Al-based alloy-coated steel sheetin accordance with an embodiment of the present invention will bediscussed below.

(Hot-Dip Al-Based Alloy-Coated Steel Sheet)

The hot-dip Al-based alloy-coated steel sheet in accordance with anembodiment of the present invention will be discussed below withreference to FIG. 1. FIG. 1 is an optical photomicrograph of a state inwhich the outermost surface of the hot-dip Al-based alloy-coated steelsheet in accordance with an embodiment of the present invention has beenpolished so that a dendrite structure is made observable.

Schematically, the hot-dip Al-based alloy-coated steel sheet is producedby dipping a substrate steel sheet in a hot-dip Al-based alloy-coatingbath, which contains aluminum as a main component, so as to form ahot-dip Al-based alloy coated layer on a surface of the substrate steelsheet. During the production, Al and iron (Fe) interdiffuse, so that anAl—Fe alloy coated layer is also formed between (on a boundary between)(i) a steel base material of the substrate steel sheet and (ii) thehot-dip Al-based alloy coated layer. On a surface of the hot-dipAl-based alloy coated layer, dendrites having grown from spangle crystalnuclei are present (see FIG. 1). The density of the spangle crystalnuclei present on the surface of the hot-dip Al-based alloy coated layerwill be discussed later.

[Substrate Steel Sheet]

The substrate steel sheet can be selected from commonly-used substratesteel sheets in accordance with a purpose for which the substrate steelsheet is used. In a case where the substrate steel sheet is used whilecorrosion resistance is considered important, a stainless steel sheet isapplicable. The substrate steel sheet can have a thickness of, forexample, 0.4 mm to 2.0 mm. The substrate steel sheet as used hereinencompasses a substrate steel strip.

[Al—Fe Alloy Layer]

The Al—Fe alloy layer is made mainly of an Al—Fe-based intermetalliccompound. Note here that the hot-dip Al-based alloy-coating bathpreferably contains silicon (Si). An Al—Fe-based alloy layer formed withuse of an Si-containing Al-based alloy-coating bath contains a largeamount of Si. Both an Si-free Al—Fe-based alloy layer and a so-calledAl—Fe—Si-based alloy layer containing Si are herein collectivelyreferred to as an Al—Fe-based alloy layer.

In a case where the Al—Fe-based alloy layer, which is made of a brittleintermetallic compound, has a greater thickness, the coated layer ismade less adhesive. This leads to inhibition of press workability. Fromthe viewpoint of press workability, the Al—Fe-based alloy layerpreferably has a thickness that is as small as possible. However, atechnique of a too large reduction in thickness of the Al—Fe-based alloylayer increases the process load, and such a technique is uneconomical.Generally, the Al—Fe-based alloy layer only needs to have an averagethickness of not less than 0.5 μm.

[Composition of Hot-Dip Al-Based Alloy Coated Layer]

The hot-dip Al-based alloy coated layer has a chemical composition thatis substantially identical to the composition of the coating bath. Thecomposition of the coated layer can thus be controlled by adjusting thecomposition of the coating bath.

Note that the hot-dip Al-based alloy coated layer, which refers to acoated layer formed on the surface of the substrate steel sheet,encompasses the Al—Fe-based alloy layer. An aluminum oxide layer formedon the topmost surface of the hot-dip Al-based alloy-coated steel sheetcauses no particular problem because the aluminum oxide layer is verythin. The aluminum oxide layer is therefore assumed to be encompassed inthe hot-dip Al-based alloy coated layer. In a case where, for example, afilm layer such as an organic film is further formed on the surface ofthe hot-dip Al-based alloy-coated steel sheet by a post treatment, sucha film layer is, as a matter of course, not encompassed in the hot-dipAl-based alloy coated layer.

As such, the “average concentration” of a substance contained in thehot-dip Al-based alloy coated layer as used herein refers to an averageof concentrations of the substance which concentrations are measured, ina direction in which the depth of the hot-dip Al-based alloy coatedlayer extends, from the surface of the substrate steel sheet of thehot-dip Al-based alloy-coated steel sheet to the outer surface of thehot-dip Al-based alloy coated layer of the hot-dip Al-based alloy-coatedsteel sheet. Specifically, as described later, the average concentrationof a substance is measured by carrying out concentration analysis withrespect to a measurement solution in which all the hot-dip Al-basedalloy coated layer has been melted. That is, the average concentrationof B, which is an element enriched on the surface of the hot-dipAl-based alloy coated layer, refers to the concentration of B containedin the hot-dip Al-based alloy coated layer, the concentration beingobtained by averaging concentrations of B assuming that no B is enrichedon the surface of the hot-dip Al-based alloy coated layer. Furthermore,the concentration of B contained in the hot-dip Al-based alloy-coatingbath is reflected in the average concentration of B contained in thehot-dip Al-based alloy coated layer formed through coating.

The hot-dip Al-based alloy coated layer at least contains B and K whilecontaining Al as a main component. Note, however, that the hot-dipAl-based alloy coated layer can contain other element(s).

Si is an additive element that is necessary for inhibition of growth ofthe Al—Fe alloy layer during hot-dip coating. The Al-based alloy-coatingbath to which Si is added has a lower melting point. This is effectivein reducing a temperature at which coating is carried out. In a casewhere the coating bath contains Si at a concentration of less than 1.0mass %, the Al—Fe-based alloy layer is formed thick during hot-dipcoating due to interdiffusion of Al and Fe. This causes peeling off inthe coated layer during processing such as press forming. Meanwhile, ina case where the coating bath contains Si at a concentration of morethan 12.0 mass %, the coated layer is cured. This makes it impossible toprevent cracking in a bent part of the coated layer and consequentlycauses the bent part to have lower corrosion resistance. Therefore, thecoating bath preferably contains Si at a concentration of 1.0 mass % to12.0 mass %. In particular, the coating bath which contains Si at aconcentration of less than 3.0 mass % (i) allows an Si phase to beformed in a smaller amount during solidification of the coated layer and(ii) allows softening of a primary crystal Al phase. Such a coating bathis thus more effective in applications in which bending workability isconsidered important.

In the hot-dip Al-based alloy-coating bath, Fe is mixed which comes fromthe substrate steel sheet and/or a constituent member(s) of a hot-dipcoating tank. Generally, the hot-dip Al-based alloy coated layercontains Fe at a concentration of not less than 0.05 mass %. Note thatFe is permitted to be contained in the hot-dip Al-based alloy coatedlayer at a concentration of up to 3.0 mass %, but more preferably notmore than 2.5 mass %.

Besides the above elements, an element(s) (such as strontium (Sr),sodium (Na), calcium (Ca), antimony (Sb), phosphorus (P), magnesium(Mg), chromium (Cr), manganese (Mn), Ti, Zr, and/or vanadium (V)) may beintentionally added to the hot-dip Al-based alloy-coating bath asnecessary, or the above element(s) coming from, for example, a rawmaterial may be mixed in the hot-dip Al-based alloy-coating bath. Thehot-dip Al-coated steel sheet in accordance with an embodiment of thepresent invention can also contain such an element that has beenconventionally commonly permitted. Specifically, for example, hot-dipAl-coated steel sheet can contain Sr at a concentration falling withinthe range of 0 mass % to 0.2 mass %, Na at a concentration fallingwithin the range of 0 mass % to 0.1 mass %, Ca at a concentrationfalling within the range of 0 mass % to 0.1 mass %, Sb at aconcentration falling within the range of 0 mass % to 0.6 mass %, P at aconcentration falling within the range of 0 mass % to 0.2 mass %, Mg ata concentration falling within the range of 0 mass % to 5.0 mass %, Crat a concentration falling within the range of 0 mass % to 1.0 mass %,Mn at a concentration falling within the range of 0 mass % to 2.0 mass%, Ti at a concentration falling within the range of 0 mass % to 0.5mass %, Zr at a concentration falling within the range of 0 mass % to0.5 mass %, and/or Vat a concentration falling within the range of 0mass % to 0.5 mass %.

The remainder, different from the foregoing elements, of the hot-dipAl-based alloy-coating bath can be constituted by Al and unavoidableimpurities.

As described earlier, a hot-dip aluminum-based alloy-coated steel sheetin accordance with an embodiment of the present invention includes: asubstrate steel sheet; and a hot-dip aluminum-based alloy coated layerwhich is formed on a surface of the substrate steel sheet and whichcontains boron at an average concentration of not less than 0.005 mass %and contains potassium at an average concentration of not less than0.0004 mass %.

In a case where the hot-dip aluminum-based alloy coated layer whichcontains B at a concentration falling within the above range andcontains K at a concentration falling within the above range, not lessthan 100 spangle crystal nuclei can be present per square centimetersurface area of the hot-dip Al-based alloy coated layer. This makes itpossible to produce a hot-dip Al-based alloy-coated steel sheet whichincludes a coated layer having a surface on which fine spangles aresufficiently formed and which has a beautiful surface appearance due tothe fine spangles thus formed on the surface of the coated layer. Such ahot-dip Al-based alloy-coated steel sheet can be obtained by (i)adjusting the respective concentrations of B and K which are containedin the coating bath and (ii) dipping the substrate steel sheet in thecoating bath. This makes it possible to achieve the hot-dip Al-basedalloy-coated steel sheet in which fine spangles are stably formed.

By referring to FIG. 1 again, the following description will discuss thedensity of spangle crystal nuclei. As illustrated in FIG. 1, thespangles are non-uniform and irregular in size. However, spangle crystalnuclei are still distinguishable when viewed through, for example, anoptical microscope.

Therefore, the number of spangle crystal nuclei per visual field areacan be understood by counting the number of spangle crystal nucleipresent in that visual field area. From the number of spangle crystalnuclei per visual field area, it is possible to roughly calculate thenumber of spangle crystal nuclei present per square centimeter surfacearea of the hot-dip Al-based alloy coated layer. Note that such acounting method as described above is merely an example, and the numberof spangle crystal nuclei can be counted by any other method.

The hot-dip Al-based alloy coated layer which contains B at an averageconcentration of less than 0.005 mass % makes it impossible to achieve asatisfactory effect of finer spangles. Meanwhile, the hot-dip Al-basedalloy coated layer which contains B at an average concentration of morethan 0.50 mass % causes the effect of finer spangles to reach a maximum,and no superiority is displayed by the hot-dip Al-based alloy coatedlayer in which the average concentration of B is further increased.

The hot-dip Al-based alloy coated layer which contains B at an averageconcentration of more than 3.0% may cause a decrease in corrosionresistance. Therefore, from the viewpoint of corrosion resistance of thehot-dip Al-based alloy-coated steel sheet, the hot-dip Al-based alloycoated layer preferably contains B at an average concentration of 0.005mass % to 3.0 mass %.

The hot-dip Al-based alloy coated layer which contains K at an averageconcentration of less than 0.0004 mass % makes it impossible to achievea satisfactory effect of finer spangles. Meanwhile, the hot-dip Al-basedalloy coated layer which contains K at an average concentration of morethan 0.05 mass % causes the effect of finer spangles to reach themaximum. The hot-dip Al-based alloy coated layer which contains K at anaverage concentration of not less than 0.03 mass % causes a decrease incorrosion resistance. Therefore, from the viewpoint of corrosionresistance of the hot-dip Al-based alloy-coated steel sheet, the hot-dipAl-based alloy coated layer preferably contains K at an averageconcentration of 0.0004 mass % to 0.02 mass %.

From the viewpoint of corrosion resistance of the hot-dip Al-basedalloy-coated steel sheet, the hot-dip Al-based alloy coated layer ispreferably configured to contain B at an average concentration of 0.005mass % to 3.0 mass % and contain K at an average concentration of 0.0004mass % to 0.02 mass %. The configuration makes it possible to produce ahot-dip Al-based alloy-coated steel sheet which has a beautiful surfaceappearance and excellent corrosion resistance.

As described earlier, the effect of finer spangles reaches the maximumin a case where the respective average concentrations of B and K whichare contained in the hot-dip Al-based alloy coated layer are increasedto some extent. Therefore, according to an embodiment of the presentinvention, it is unnecessary to set respective upper limits of thoseconcentrations.

The hot-dip Al-based alloy coated layer is preferably configured tocontain B at an average concentration of not less than 0.02 mass % andcontain K at an average concentration of not less than 0.0008 mass %.The configuration allows not less than 200 spangle crystal nuclei to bepresent per square centimeter surface area of the hot-dip Al-based alloycoated layer. This makes it possible to produce a hot-dip Al-basedalloy-coated steel sheet which has a more beautiful surface appearance.

The hot-dip Al-based alloy coated layer of the hot-dip Al-basedalloy-coated steel sheet does not necessarily need to be provided onboth sides of the substrate steel sheet, and only needs to be providedon at least one side of the substrate steel sheet.

(Method of Producing Hot-Dip Al-Based Alloy-Coated Steel Sheet)

A hot-dip Al-based alloy-coated steel sheet in accordance with anembodiment of the present invention can be produced by a hot-dip methodwith use of a coating bath containing B and K at respective adjustedconcentrations. For example, the hot-dip Al-based alloy-coated steelsheet can be produced in an experimental line and by a common continuousAl-coating production process (production apparatus). Alternatively, thehot-dip Al-based alloy-coated steel sheet in accordance with anembodiment of the present invention can be produced by applying thepresent invention to any method, known to a skilled person, of producinga hot-dip Al-coated steel sheet.

A method of producing a hot-dip aluminum-based alloy-coated steel sheetin accordance with an embodiment of the present invention includes acoating step of dipping a substrate steel sheet in a hot-dipaluminum-based alloy-coating bath which contains aluminum as a maincomponent, the hot-dip aluminum-based alloy-coating bath containingboron at a concentration of not less than 0.005 mass % and containingpotassium at a concentration of not less than 0.0004 mass %.

The average concentration of each component contained in the hot-dipAl-based alloy coated layer formed through the coating step issubstantially identical to the composition of the hot-dip Al-basedalloy-coating bath (i.e., the concentration of each component containedin the hot-dip Al-based alloy-coating bath). The configuration makes itpossible to produce a hot-dip Al-based alloy-coated steel sheetincluding a hot-dip Al-based alloy coated layer which contains B at anaverage concentration of not less than 0.005 mass % and contains K at anaverage concentration of not less than 0.0004 mass %.

From this, it is preferable that, as with the hot-dip Al-basedalloy-coated steel sheet, the hot-dip Al-based alloy-coating bathcontain B at a concentration of not less than 0.02 mass % and contain Kat a concentration of not less than 0.0008 mass %. Note that the hot-dipAl-based alloy-coating bath preferably contains B at a concentration of0.005 mass % to 3.0 mass %. Note also that the hot-dip Al-basedalloy-coating bath preferably contains K at a concentration of 0.0004mass % to 0.02 mass %.

At least prior to the coating step, a composition adjusting step ofadjusting a composition of the hot-dip Al-based alloy-coating bath iscarried out by adjusting respective concentrations of elements containedin the hot-dip Al-based alloy-coating bath. In the composition adjustingstep, the composition of the hot-dip Al-based alloy-coating bath can beadjusted as below.

The concentration of B contained in the hot-dip Al-based alloy-coatingbath is preferably configured to be adjusted by adding an aluminummaster alloy containing B. The configuration allows suitable dispersionof B in the hot-dip Al-based alloy-coating bath. The concentration of Bcontained in the hot-dip Al-based alloy-coating bath can alternativelybe adjusted by adding B alone or a boride such as aluminum boride (AlB₂or AlB₁₂), and a method of adjusting the concentration is not limited toany particular method. The hot-dip Al-based alloy-coating bath whichcontains such a raw material needs to be subjected to a process foruniformly dispersing B in the hot-dip Al-based alloy-coating bath.

Similarly, the concentration of K contained in the hot-dip Al-basedalloy-coating bath is preferably configured to be adjusted by adding analuminum master alloy containing K. The configuration allows suitabledispersion of K in the hot-dip Al-based alloy-coating bath. Theconcentration of K contained in the hot-dip Al-based alloy-coating bathcan alternatively be adjusted by adding K alone or a compound such asKF, KBF₄, or K₂AlF₆AlB₂, and a method of adjusting the concentration isnot limited to any particular method. The hot-dip Al-based alloy-coatingbath which contains such a raw material needs to be subjected to aprocess for uniformly dispersing K in the hot-dip Al-based alloy-coatingbath.

The respective concentrations of B and K which are contained in thehot-dip Al-based alloy-coating bath are preferably configured to beadjusted by adding an aluminum master alloy containing B and K. With theconfiguration, the addition of such an aluminum master alloy allows Band K to be easily and suitably dispersed in the hot-dip Al-basedalloy-coating bath. In this case, the respective concentrations of B andK which are contained in the aluminum master alloy have a ratio that issubstantially equal to a ratio between the respective concentrations ofB and K which are contained in the hot-dip Al-based alloy-coating bath.Alternatively, the respective concentrations of B and K which arecontained in the hot-dip Al-based alloy-coating bath can be configuredto be adjusted as desired by adding a plurality of aluminum masteralloys which differ from each other in amount of B contained and inamount of K contained. The configuration can be summarized as below. Themethod of producing the hot-dip aluminum-based alloy-coated steel sheetpreferably further includes a composition adjusting step of adjusting acomposition of the hot-dip aluminum-based alloy-coating bath, thecomposition adjusting step including adding an aluminum master alloycontaining boron and potassium.

In a case where the hot-dip Al-based alloy-coating bath contains Si, theconcentration of Si is preferably adjusted by adding an aluminum masteralloy containing Si. Furthermore, it is only necessary that otherelement(s) that can be contained in the hot-dip Al-based alloy-coatingbath be added by a well-known method so that a concentration(s) of theelement(s) is/are adjusted.

Note here that an industrial continuous Al-coating producing apparatusis configured such that substrate steel sheets are continuously dippedin a hot-dip Al-based alloy-coating bath so that hot-dip Al-basedalloy-coated steel sheets are continuously produced. During theproduction, each component contained in the hot-dip Al-basedalloy-coating bath is gradually reduced by an amount in which thesubstrate steel sheets are coated with the each component. This makes itnecessary to compensate for the reduction in hot-dip Al-basedalloy-coating bath by any method.

As described earlier, the respective concentrations of B and K which arecontained in the hot-dip Al-based alloy-coating bath can be adjusted byadding an aluminum master alloy containing B and K. This makes itpossible to easily compensate for the reduction in hot-dip Al-basedalloy-coating bath by using an aluminum master alloy containing B and Kin desired amounts, or using a plurality of aluminum master alloys whichdiffer from each other in amount B contained and in amount of Kcontained. In a case where the hot-dip Al-based alloy-coating bathcontains Si, it is only necessary to simultaneously add an aluminummaster alloy containing Si. By thus carrying out the compositionadjusting step concurrently with the coating step, it is possible tocontinuously and stably produce hot-dip Al-based alloy-coated steelsheets each having a beautiful surface appearance.

As described earlier, a hot-dip aluminum-based alloy-coated steel sheetin accordance with an embodiment of the present invention includes: asubstrate steel sheet; and a hot-dip aluminum-based alloy coated layerwhich is formed on a surface of the substrate steel sheet and whichcontains boron at an average concentration of not less than 0.005 mass %and contains potassium at an average concentration of not less than0.0004 mass %.

The hot-dip aluminum-based alloy-coated steel sheet in accordance withan embodiment of the present invention is configured such that not lessthan 100 spangle crystal nuclei are present on a surface of the hot-dipaluminum-based alloy coated layer per square centimeter surface area ofthe hot-dip aluminum-based alloy coated layer.

The hot-dip aluminum-based alloy-coated steel sheet in accordance withan embodiment of the present invention is preferably configured suchthat the hot-dip aluminum-based alloy coated layer contains boron at anaverage concentration of not less than 0.02 mass % and containspotassium at an average concentration of not less than 0.0008 mass %.

A method of producing a hot-dip aluminum-based alloy-coated steel sheetin accordance with an embodiment of the present invention includes acoating step of dipping a substrate steel sheet in a hot-dipaluminum-based alloy-coating bath which contains aluminum as a maincomponent, the hot-dip aluminum-based alloy-coating bath containingboron at a concentration of not less than 0.005 mass % and containingpotassium at a concentration of not less than 0.0004 mass %.

The method of producing the hot-dip aluminum-based alloy-coated steelsheet in accordance with an embodiment of the present invention ispreferably configured such that the hot-dip aluminum-based alloy-coatingbath contains boron at a concentration of not less than 0.02 mass % andcontains potassium at a concentration of not less than 0.0008 mass %.

The method of producing the hot-dip aluminum-based alloy-coated steelsheet in accordance with an embodiment of the present inventionpreferably further includes a composition adjusting step of adjusting acomposition of the hot-dip aluminum-based alloy-coating bath, thecomposition adjusting step including adding an aluminum master alloycontaining boron and potassium.

The present invention is not limited to the embodiments, but can bealtered by a skilled person in the art within the scope of the claims.The present invention also encompasses, in its technical scope, anyembodiment derived by combining technical means disclosed in differingembodiments.

EXAMPLES

A hot-dip Al-based alloy-coated steel sheet (test sample) was producedas below in an experimental line with use of coating experimentalequipment by using, as a substrate steel sheet, a cold-rolled annealedsteel sheet having a thickness of 0.8 mm and having the chemicalcomposition shown in Table 1. Specifically, the hot-dip Al-basedalloy-coated steel sheet was produced by (i) dipping the substrate steelsheet in a hot-dip Al-based alloy-coating bath prepared as describedlater, (ii) taking out the substrate steel sheet thus dipped, and (iii)solidifying a coated layer at a given cooling rate.

As the hot-dip Al-based alloy-coating bath, hot-dip Al-basedalloy-coating baths having various compositions were prepared as below.

The concentration of Si contained in the coating bath was adjusted to 0mass % to 14.0 mass % with use of an Al-20 mass % Si master alloy (an Almaster alloy containing Si at a concentration of 20 mass %). Then, theconcentration of B contained in the coating bath was adjusted to 0 mass% to 3.0 mass % by adding, to the coating bath, a given amount of anAl-4 mass % B master alloy (an Al master alloy containing B at aconcentration of 4 mass %). Furthermore, the concentration of Kcontained in the coating bath was adjusted to 0.0001 mass % to 0.05 mass% by adding a given amount of KF to the coating bath. Assuming that Fecoming from the substrate steel sheet and/or a constituent member(s) ofa pot during continuous production was unavoidably mixed in the coatingbath, the concentration of Fe contained in the coating bath was adjustedto 2.0 mass % by melting, in the coating bath, the cold-rolled annealedsteel sheet serving as the substrate steel sheet. The remainder of thecoating bath was constituted by Al and unavoidable impurities.

The substrate steel sheet was dipped in the coating bath, set at atemperature of 650° C. to 680° C., for two seconds, was taken out of thecoating bath, and then was cooled at a cooling rate of 13° C./sec.Respective amounts (concentrations) of Si, B, and K which were containedin the coated layer of each Example are shown in Table 2. Coating had,per surface thereof, a thickness of approximately 20 μm.

TABLE 1 Chemical composition (mass %) C Si Mn P S Al O N 0.033 <0.010.23 <0.01 0.013 0.01 0.0027 0.0025A resultant coated steel sheet was subjected to the followingexaminations.

(Analysis of Components of Coated Layer by ICP)

First, the coated layer was melted by the following procedure so thateach component of the coated layer was quantified.

Test samples produced with use of the foregoing hot-dip Al-basedalloy-coating baths having various compositions were each cut into apiece having a given size, so that a test sample piece was prepared. Thetest sample piece was put into an NaOH solution (10 ml) at aconcentration of 25%, was left to stand still, and then was heated sothat the coated layer was completely melted in the solution. After itwas confirmed that the coated layer had been completely melted, the testsample piece, from which the coated layer had been removed by beingmelted, was taken out of the solution. Subsequently, the solution wasfurther heated so that the liquid was evaporated to dryness. A productobtained as a result of evaporation to dryness was dissolved in a mixedacid (a mixed solution of 40 ml of nitric acid and 10 ml of hydrochloricacid) while being heated, and ultrapure water was added to a resultantsolution so that the volume of the solution was adjusted to a constantvolume of 250 ml. The solution which had been obtained from the testsample piece and whose volume had been thus made constant was used as asolution for use in measurement of the composition of each test sample.

Thereafter, the solution for use in measurement of the composition ofeach test sample was subjected to the following two types ofquantitative analyses so that the composition of the coated layer wasfound.

The quantitative analysis of Si, B, and Fe was carried out by aninductively coupled plasma atomic emission spectrometry method (ICP-AESmethod). The quantitative analysis of K was carried out by aninductively coupled plasma mass spectrometry method (ICP-MS method).

(Number of Spangle Crystal Nuclei on Surface of Coated Layer)

A dendrite structure was made observable by buffing the surface of eachtest sample so as to make smoother the outermost surface layer extendingfrom the surface of the coated layer to the depth of 5 μm. Then, thenumber of spangle crystal nuclei present per square centimeter surfacearea of the coated layer was calculated with use of an opticalmicroscope. The coated layer was evaluated based on the followingcriteria, and the coated layer evaluated as “Good” or “Excellent” wasregarded as acceptable.

Excellent: Not less than 200 spangle crystal nuclei were present persquare centimeter surface area of the coated layer.Good: Not less than 100 and less than 200 spangle crystal nuclei werepresent per square centimeter surface area of the coated layer.Poor: Not less than 50 and less than 100 spangle crystal nuclei werepresent per square centimeter surface area of the coated layer.Very Poor: Less than 50 spangle crystal nuclei were present per squarecentimeter surface area of the coated layer.

(Corrosion Resistance of Coated Layer)

An untreated hot-dip Al-based alloy coated layer of each test sample wassubjected to a neutral salt spray test (NSS test), specified by JISZ2371:2000, so that a ratio of an area of white rust formation to theentire coated layer was measured. Corrosion resistance of the coatedlayer was evaluated based on the following criteria, and the coatedlayer evaluated as “Good” was regarded as acceptable.

Good: The ratio of the area of white rust formation to the entire coatedlayer was not less than 0% and less than 5%.Fair: The ratio of the area of white rust formation to the entire coatedlayer was not less than 5% and less than 20%.Poor: The ratio of the area of white rust formation to the entire coatedlayer was not less than 20%.

Results of the above examinations are shown in Table 2.

TABLE 2 Amount (Concentration) of Component Contained in Coating LayerDensity of Grade of (mass %) Spangles Surface Corrosion Class No. Si B K(per cm²) Appearance Resistance Examples of 1 0 0.01 0.0004 120 GoodGood present 2 0.5 0.02 0.0005 150 Good Good invention 3 1 0.02 0.0005150 Good Good 4 2 0.025 0.0008 400 Excellent Good 5 3 0.02 0.0008 200Excellent Good 6 5 0.02 0.0008 200 Good Good 7 8.8 0.018 0.0005 180 GoodGood 8 8.9 0.01 0.0004 120 Good Good 9 9 0.02 0.0004 150 Good Good 109.1 0.02 0.0008 200 Excellent Good 11 9.2 0.02 0.0015 200 Excellent Good12 9.2 0.05 0.002 500 Excellent Good 13 9.5 0.5 0.02 500 Excellent Good14 10 1 0.02 200 Excellent Good 15 12.3 2 0.02 200 Excellent Good 1613.1 0.03 0.02 400 Excellent Good 17 5 3 0.02 500 Excellent Good 18 90.022 0.03 300 Excellent Poor 19 9.2 0.05 0.05 500 Excellent PoorComparative 20 2 0.002 0.0004 20 Very Poor Good Examples 21 8.8 0.020.0001 60 Poor Good 22 9 0.02 0.0003 80 Poor Good 23 9.2 0 0.0001 5 VeryPoor Good 24 12 0 0.0004 5 Very Poor Good 25 9.2 0.002 0.0001 8 VeryPoor Good 26 9.5 0.015 0.0001 70 Poor Good 27 9 0.022 0.0001 60 PoorGood 28 8.9 0.03 0.0001 70 Poor Good 29 9.1 0.05 0.0001 80 Poor Good

As shown in Nos. 1 to 19 of Table 2, according to Examples in each ofwhich the coated layer contained B and K at respective averageconcentrations falling within the ranges defined by an embodiment of thepresent invention, not less than 100 spangle crystal nuclei were presentper square centimeter surface area of the coated layer. This broughtabout a good effect of finer spangles. Examples of the present inventionreveal that an embodiment of the present invention makes it possible toobtain a hot-dip Al-based alloy-coated steel sheet which includes acoated layer having a surface on which fine spangles are stably andsufficiently formed and which has a beautiful surface appearance due tothe fine spangles thus formed on the surface of the coated layer.

Examples of Nos. 4, 5, and 10 to 19 reveal (i) that not less than 200spangle crystal nuclei were present per square centimeter surface areaof the coated layer which contained B at an average concentration of notless than 0.02 mass % and contained K at an average concentration of0.0008 mass % and (ii) that such a coated layer makes it possible toobtain a hot-dip Al-based alloy-coated steel sheet which has a morebeautiful surface appearance.

Examples of Nos. 1 to 17 reveal that the coated layer which contained Kat an average concentration of 0.0004 mass % to 0.02 mass % had goodcorrosion resistance and makes it possible to obtain a hot-dip Al-basedalloy-coated steel sheet which has a beautiful surface appearance andhas excellent corrosion resistance.

In contrast, according to Comparative Examples Nos. 20 to 29 in each ofwhich the coated layer contained B and K at respective averageconcentrations outside (less than lower limits of) the ranges defined byan embodiment of the present invention, less than 100 spangle crystalnuclei were present per square centimeter surface area of the coatedlayer. This (i) revealed that the effect of finer spangles was not goodenough and (ii) resulted in obtainment of the hot-dip Al-basedalloy-coated steel sheets each having a poor surface appearance.

Note that, as shown in Nos. 1 to 29 of Table 2, the averageconcentration of Si contained in the coated layer did not particularlyaffect the effect of the present invention.

1-3. (canceled)
 4. A method of producing a hot-dip aluminum-based alloy-coated steel sheet, comprising: a coating step of dipping a substrate steel sheet in a hot-dip aluminum-based alloy-coating bath which contains aluminum as a main component, the hot-dip aluminum-based alloy-coating bath containing boron at a concentration of not less than 0.005 mass % and not more than 3.0 mass % and containing potassium at a concentration of not less than 0.0004 mass % and not more than 0.02 mass %.
 5. The method as set forth in claim 4, wherein the hot-dip aluminum-based alloy-coating bath contains boron at a concentration of not less than 0.02 mass % and not more than 3.0 mass % and contains potassium at a concentration of not less than 0.0008 mass % and not more than 0.02 mass %.
 6. The method as set forth in claim 4, further comprising: a composition adjusting step of adjusting a composition of the hot-dip aluminum-based alloy-coating bath, the composition adjusting step including adding an aluminum master alloy containing boron and potassium.
 7. The method as set forth in claim 5, further comprising: a composition adjusting step of adjusting a composition of the hot-dip aluminum-based alloy-coating bath, the composition adjusting step including adding an aluminum master alloy containing boron and potassium. 